Metal sorption on macroporous poly(GMA-co-EGDMA) modified with ethylene diamine

Two samples of macroporous crosslinked poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate), poly(GMA-co-EGDMA), with different porosity parameters were synthesized by suspension copolymerization and modified by ring-opening reaction of the pendant epoxy groups with ethylene diamine (EDA). The samples were characterized by mercury porosimetry, FT-IR spectroscopy and elemental analysis. The sorption rate of the modified copolymer, poly(GMA-co-EGDMA)-en for Cu(II) ions determined under non-competitive conditions was relatively rapid, i.e. the maximum capacity was reached within 30 min. Batch sorption capacities for Cu(II), Fe(II), Mn(II), Cd(II), Zn(II), Pb(II), Cr(III) and Pt(IV) ions were determined under non-competitive conditions in the pH range 1.25–5.5 at room temperature. The maximum sorption capacities of poly(GMA-co-EGDMA)-en under non-competitive conditions were 1.30 mmol/g for Pt(IV) at pH 5.5, 1.10 mmol/g for Cu(II) at pH 5.5, 1.06 mmol/g for Pb(II) at pH 1.25 and 0.67 mmol/g for Cd(II) ions at pH 5.5. The selectivity of poly(GMA-co-EGDMA)-en towards Cu(II), Co(II), Ni(II), Pb(II) and Pt(IV) ions was investigated under competitive conditions. Poly(GMA-co-EGDMA)-en showed high selectivity for Pt(IV) over Cu(II), Co(II), Ni(II) and Pb(II) ions at pH 2.1. At pH 5.5, the metal sorption capacities of poly(GMA-co-EGDMA)-en decreased in the order: Cu(II) > Co(II) > Pt(IV) ≈ Ni(II) > Pb(II). Regeneration of the Cu(II), Ni(II) and Pb(II) loaded poly(GMA-co-EGDMA)-en with 2 M H₂SO₄ showed that the polymer can be reused in several sorption/desorption cycles.     

A novel agricultural waste based adsorbent for the removal of Pb(II) from aqueous solution: Kinetics,equilibrium and thermodynamic studies

Fig sawdust was used as a precursor for the production of activated carbon by chemical activation with H₃PO₄. The developed Fig sawdust activated carbon (FSAC) was used as a biosorbent for the removal of Pb(II) from aqueous solution. Highest adsorption of Pb(II) (95.8%) was found at pH 4. Equilibrium data fitted very well with the Langmuir isotherm model. Maximum adsorption capacity was determined 80.645 mg g⁻¹ at pH 4. Kinetic studies demonstrated that the adsorption followed a pseudo second order kinetics model. The negative value of ΔG° confirmed the feasibility and spontaneity of FSAC for Pb(II) adsorption.     

Multilayer 0.9Pb(Mg1/3Nb2/3)O3–0.1PbTiO3 elements for electrocaloric cooling

Electrocaloric (EC) cooling elements in the form of multilayers (MLs) were prepared. The elements consist of five layers of the relaxor-ferroelectric 0.9Pb(Mg_1/3Nb_2/3)O₃–0.1PbTiO₃, about 60 μm thick, with internal platinum electrodes and exhibiting a dense, uniform microstructure with a grain size of 1.7 μm. The largest temperature change ΔT_EC of 2.26 K was achieved at an electric field (E) of 100 kV cm⁻¹ and at 105 °C, measured by a high-resolution calorimeter. These results agree well with the indirect measurements. The EC coefficient, ΔT_EC/ΔE, obtained for the MLs, is similar to the value obtained for bulk ceramics of the same composition. The ΔT_EC values above 2 K over a broad temperature range from 75 to 105 °C make the ML elements suitable candidates for EC cooling devices at significantly lower voltages than bulk ceramic plates with comparable dimensions and mass.     

Modeling moisture sorption isotherms in roasted green wheat using least square regression and neural-fuzzy techniques

Roasted green wheat at moisture content from 0.052 to 0.25 (decimal d.b.) and temperatures from 25 to 43 °C was used to model moisture sorption isotherms using conventional non-linear least square regression (NLR) and neural-fuzzy (NF) techniques. The results showed that neural-fuzzy techniques provided a better fit than conventional least square regression with: R² = 0.99 and 0.97, RMSE = 0.01 and 0.0038, E% = 1.01 and 5.9 and SSE = 0.0008 and 0.009, for NF and NLR techniques, respectively. Differential enthalpy decreased from 477.9 kJ/kg at 0.052 (decimal d.b. mc) to 44.7 kJ/kg at 0.25 (decimal d.b. mc) and entropy decreased from 1.16 kJ/kg K at 0.052 (decimal d.b. mc) to 0.014 kJ/kg K at 0.25 (decimal d.b. mc). A linear plot between enthalpy and entropy showed that compensation exists. The isokinetic temperature T_β was 376.13 K which was larger than the harmonic mean temperature T_hm = 307.31 K, showing that the water sorption was entropy-driven. The free energy change ΔG was positive (+38.42 kJ/kg) indicating a non-spontaneous water sorption process.     

Temperature and alkaline hydroxide treatment effects on hydrogen sorption characteristics of multi-walled carbon nanotube–graphite mixture

Temperature and alkaline hydroxide treatment effects on the surface area and pore structure of the cathode deposit multi-walled carbon nanotube (MWCNT)–graphite mixture were investigated in a temperature range of 600–800 °C. Hydrogen sorption properties of the MWCNT–graphite mixture samples were studied by varying the alkaline hydroxide-activation temperature. Pore characterization of modified MWCNT–graphite mixture was performed with the observation of adsorption–desorption isotherms of N₂ at 77 K. Hydrogen sorption of the non-treated and treated MWCNT–graphite mixture was carried out using a volumetric apparatus at 77 K. The highest surface area of the sample was obtained as 275 m² g^?1 by treatments with KOH at 600 °C. The increase in the specific surface area of MWCNT–graphite sample mixture was about 13 times. The maximum amount of hydrogen adsorbed on the MWCNT–graphite sample mixture was found as 0.75 and 0.54 wt.% by chemical treatments with KOH at 600 °C and NaOH at 700 °C, respectively whereas it was 0.01 wt.% for the original sample. The hydrogen sorption capacity was enhanced considerably by KOH treatments at 600 °C.     

Mercury(II) removal from aqueous solution by sorption onto alginate,pectate and polygalacturonate calcium gel beads. A kinetic and speciation based equilibrium study

Gel beads of calcium alginate, pectate and polygalacturonate salts have been tested as sorbent materials for mercury(II) removal from aqueous solutions. Physico-chemical properties of gel beads, defined by SEM–EDX, TGA and texture and density analysis, were correlated with gel beads sorption capacity towards Hg²⁺ ion. A speciation study in aqueous solution was carried out to define the strength of interaction of mercury ion with the polymers investigated and to assess the more suitable experimental conditions to achieve the best effectiveness of Hg²⁺ sorption by gel beads. On the basis of the speciation study, pH values in the 3–5.5 pH range were considered appropriated for mercury(II) sorption by gel beads. Kinetics of mercury(II) sorption and calcium(II) release from the sorbent materials were studied at pH 3, 3.6 and 5.2. The highest sorption rate (K) and amount of mercury(II) adsorbed were obtained at pH 3 and 3.6; therefore, pH 3.3 was chosen for the equilibrium study of Hg²⁺ sorption at 25 °C. The results obtained by using Langmuir and Freundlich isotherm equations show the following sorption capacity trend: Ca–Pect > Ca–PGA > Ca–AA.     

A novel Co-ions complexation method to synthesize pyrochlore La2Zr2O7

Pure pyrochlore Lanthanum zirconate (LZ) was synthesized by co-ions complexation method (CCM) at 1300 °C, which is 300 °C lower than that by solid-state method (SSM). At 1450 °C, the LZ prepared by CCM possessed lower thermal conductivity (1.15 W/m K) than that obtained by SSM (1.99 W/m K). This significant decrease may be caused by the different grain size, which is 300 nm and 2.5 μm synthesized by CCM and SSM, respectively. LZ precursor was belt-shaped and the belt shorten and the grain grown with the temperature increasing. Fourier transform infrared spectroscopy suggested the solidification in CCM forms from the complexation between La³⁺, Zr⁴⁺ and CH₃COO⁻, which is the key for solidification. Compared to SSM, CCM is a lower temperature and simpler technology to synthesize nano-size LZ and other rare-earth oxides.     

Kinetics,equilibrium and thermodynamic studies on biosorption of hexavalent chromium by dead fungal biomass of marine Aspergillus niger

Quite a number of reports are available on metal binding capacity of different groups of microorganisms. However, reports on the equilibrium studies on biosorption by marine fungi are quite inadequate. The present study was carried out in a batch system using dead biomass of marine Aspergillus niger for the sorption of Cr(VI). The removal rate of Cr(VI) was increased with a decrease in pH and an increase in Cr(VI) and biomass concentration. A. niger exhibited the highest Cr(VI) uptake of 117.33 mg g^?1 of biomass at pH 1.0 in the presence of 400 mg l^?1 Cr at 50 °C. Kinetics studies based on fractional power, zero order, first order, pseudo-first order, Elovich, second order and pseudo-second order rate expressions have also been carried out. The experimental data were analyzed using five, two-parameter isotherms (Langmuir, Freundlich, Dubinin–Radushkevich, Temkin and Halsey). It was observed that Langmuir model exhibited the best fit to experimental data. Thermodynamic parameters of the biosorption (ΔG°, ΔH° and ΔS°) were also determined.     

Na-feldspar (F) and kaolinite (K) system at high temperature: Resulting phase composition,micro-structural features and mullite-glass Gibbs energy of formation,as a function of F/K ratio and kaolinite crystallinity

The system Na-feldspar (F) and kaolinite (K) was investigated at temperatures of interest in ceramic applications (1200–1280 °C) to study the effects of F/K ratios by weight and crystallinity degree of kaolinite on the final product, micro-structural features and mullite-glass Gibbs energy of formation (ΔG^eff). Mullite and glass are the dominant phases; in general, the higher the temperature, the larger the former. An F/K increase promotes the formation of glass and secondary mullite, appearing along with the primary one. ΔG^eff was modelled by α(T) × (F/K)² + β(T) × F/K + γ(T), α, β and γ being linear functions of temperature whose coefficients were determined by fitting the ΔG^eff-theoretical to the ΔG^eff-obtained from the measured phase compositions. ΔG^eff is less affected by temperature than by F/K, whose increase shifts equilibrium towards glass phases. The ΔG^eff-curves for ordered and disordered kaolinite intersect one another at F/K ～0.5, a ratio close to that used in industrial practice.     

Adsorption Behavior of Rhodamine B on UiO-66

The adsorption characteristics of UiO-66 (a Zr-containing metal–organic framework formed by terephthalate) for Rhodamine B (RhB), such as isotherms, kinetics and thermodynamics, were investigated systematically. The batch adsorption data conform well to the Langmuir and Freundlich isotherms. The adsorption kinetics of UiO-66 for RhB can be well described by the pseudo first-order model, and the adsorption thermodynamic parameters ΔG₀, ΔH₀ and ΔS₀ at 273 K are − 6.282 kJ·mol^− 1, 15.096 kJ·mol^− 1 and 78.052 J·mol^− 1·K^− 1, respectively. The thermodynamic analyses show that the adsorption process of RhB on UiO-66 is more favorable at higher temperatures. UiO-66 can be regenerated by desorbing in DMF solution with ultrasonic for 1 h. UiO-66 can keep good performance for at least six cycles of sorption/desorption.     

Synthesis of mesoporous molecular sieves as catalytic template for the growth of single walled carbon nanotubes

Mesoporous Mo MCM-41 and Nb MCM-41 molecular sieves were synthesized in various ratios by hydrothermal method and were characterized by XRD, N₂ adsorption isotherm and DRS-UV spectroscopy. The calcined samples were used as catalysts for the growth of carbon nanotubes using acetylene by chemical vapor deposition technique at 700–900 °C. The deposited carbon materials by acetylene decomposition, were found to be more in the case of Nb MCM-41 than in Mo MCM-41, and their catalytic activity was found to be in the order as Si/Nb = 100 > 75 > 50 > 25, and the same trend is followed for Mo MCM-41 molecular sieves. The catalytically synthesised carbon materials were characterized with Raman spectroscopy, SEM and TEM. We have obtained single walled carbon nanotubes in bundles with a tube diameter of 1.06–2.9 nm and 1.08–2.3 nm formed over Mo MCM-41 and Nb MCM-41, respectively, according to Raman spectra. Similarly well graphitised single walled carbon nanotubes formation was observed from TEM. From this observation, it is confirmed that Mo MCM-41 (100) and Nb MCM-41 (100) exist as stable catalysts for the synthesis of single walled nanotube.     

H2/D2 adsorption and desorption studies on carbon molecular sieves with different pore structures

The critical effect of confinement on the interaction of hydrogen isotopes (H₂ and D₂) with carbon surfaces was investigated through a combined low temperature adsorption/thermal desorption spectroscopy (TDS) study on three carbon molecular sieves (CMS) possessing nanopores with nominal sizes between 0.3 and 0.5 nm. The porous structure and the sorption properties of all three adsorbents were characterized by N₂ (77 K) and CO₂ (273 K), as well as H₂ and D₂ (77 K) low pressure (up to 1 bar) adsorption measurements. The interaction of the carbons with hydrogen, deuterium, and an isotopic H₂/D₂ gas mixture was further studied by means of TDS measurements, extended to temperatures down to 20 K. The differences in the H₂/D₂ adsorption/desorption profiles of the three CMS samples are correlated with the respective micropore size distributions. The presence of very narrow micropores, with size close to the kinetic diameter of the hydrogen molecule, resulted in enhanced hydrogen (both for H₂ and D₂) interactions, giving rise to a TDS maximum centered on 122 K, the highest desorption temperature ever measured for the desorption of physisorbed hydrogen. Furthermore, the quantum effects on hydrogen/deuterium adsorption on CMS adsorbents have been addressed for the first time using the TDS technique.     

Solubility and diffusion coefficient of supercritical-CO2 in polycarbonate and CO2 induced crystallization of polycarbonate

The solubility and diffusion coefficient of supercritical CO₂ in polycarbonate (PC) were measured using a magnetic suspension balance at sorption temperatures that ranged from 75 to 175 °C and at sorption pressures as high as 20 MPa. Above certain threshold pressures, the solubility of CO₂ decreased with time after showing a maximum value at a constant sorption temperature and pressure. This phenomenon indicated the crystallization of PC due to the plasticization effect of dissolved CO₂. A thorough investigation into the dependence of sorption temperature and pressure on the crystallinity of PC showed that the crystallization of PC occurred when the difference between the sorption temperature and the depressed glass transition temperature exceeded 40 °C (T − T_g ≥ 40 °C). Furthermore, the crystallization rate of PC was determined according to Avrami's equation. The crystallization rate increased with the sorption pressure and was at its maximum at a certain temperature under a constant pressure.     

Enhanced fluoride removal from water by non-thermal plasma modified CeO2/Mg–Fe layered double hydroxides

A novel fast and efficient adsorbent based on lamellar compound namely CeO₂/Mg–Fe layered double hydroxide composite has been designed for fluoride removal from water. In order to improve fluoride removal efficiency, non-thermal plasma (NTP) was used to modify the surface state of composites. The prepared composites were characterized by powder X-ray diffraction, thermogravimetric analysis and surface area analyzer. Adsorption equilibrium and kinetics of fluoride on NTP modified composites were investigated. Experimental results indicated that the adsorption capacity was enhanced with NTP surface modification. The maximum adsorption capacity has been found to be 38.7–60.4 mg/g. The kinetic data of adsorption were found to best fit the pseudo-second-order model, while the equilibrium data were found to be well described by Langmuir model. In order to understand the mechanism of adsorption, thermodynamic parameters such as ΔG^θ, ΔS^θ and E_a were calculated. After NTP treatment, the ΔS^θ increased from − 34.7 J/mol·K to − 0.770 J/mol·K, the E_a decreased from 78.8 kJ/mol to 58.9 kJ/mol and the ΔG^θ (25 °C) decreased from − 2.62 kJ/mol to − 3.14 kJ/mol. These values indicate that the fluoride adsorption on NTP modified composites was improved.     

Electrocaloric and pyroelectric properties of PZT and PMN–PNN–PZT thin films

The electrocaloric effects (EC) of PZT and PMN–PNN–PZT films were evaluated. PZT and PMN–PNN–PZT thin films with a thickness of 500 nm were fabricated by state-of-the-art chemical solution deposition from a precursor solution with PZT and (PMN?PNN)/PZT=30/70. The polarization hysteresis loop was found to be slim and nonlinear, with smaller hysteretic behavior compared with PZT. The pyroelectric properties evaluated from polarization change and current measurement show that the properties of PMN–PNN–PZT films are superior to those of non-doped PZT films. The electrocaloric temperature changes ΔT due to applied ΔE were calculated. PZT and PMN–PNN–PZT films exhibited ΔT of 2.1 K and 3.6 K at 237.5 °C under a field of 500 kV/cm, respectively. Thermal-electrical energy converters based on pyroelectric effects were investigated for energy harvesting and possible use in ultralow-power sensor modules. The possibilities of pyroelectric energy harvesting using these PZT films were also investigated.     

Adsorption of Pb(II) from aqueous solution to Ni-doped bamboo charcoal

Bamboo charcoal (BC) obtained by pyrolysis of Makino bamboo in the absence of oxygen was used as support for the preparation of Ni-doped adsorbent (Ni-BC). The low-cost composite was characterized and used as an adsorbent for Pb(II) removal from water. The results showed that both BET surface area and total pore volume of Ni-BC increased. The adsorption of Pb(II) strongly depended on solution pH, temperature and ionic strength. The adsorption isotherms followed Langmuir isotherm model well, and the maximum adsorption capacities of Pb(II) at 298 K were 25.0 and 142.7 mg/g for BC and Ni-BC, respectively. The adsorption processes were well fitted by pseudo-second-order kinetic model. Thermodynamic parameters showed that the adsorptions of Pb(II) onto both adsorbents were feasible, spontaneous, and exothermic under the studied conditions. The spent Ni-BC could be readily regenerated for reuse.     

Hygroscopic behavior of banana (Musa ssp. AAA) flour in different ripening stages

The objective of this study was to evaluate the hygroscopic behavior of ‘Nanicão’ banana flour at three ripening stages (2–9 °Brix) using moisture sorption isotherms at 25 °C. The flour samples were obtained using a fixed-bed drying process at 60 °C. The BET monolayer procedure was used for the desorption analysis. The Halsey, Henderson, Oswin, Smith, BET and GAB models were fitted to the sorption data. All flours exhibited type II isotherms that were almost superimposed, indicating that the ripening stage of the banana did not alter the hygroscopic behavior of the products. According to the adsorption isotherms, the flour has microbiological stability (a_w < 0.6) at moisture contents below 13 g H₂O/100 g dry base (d.b.). The monolayer moisture content indicated that the drying process of the ‘Nanicão’ banana should not proceed to moisture content lower than 7.10 g H₂O/100 g d.b. to avoid unnecessary power consumption. A type-H3 hysteresis between the adsorption and desorption isotherms of flour was observed. The Oswin, Smith and GAB models provided the best fit for the flour adsorption and desorption data.     

Sorption of heavy metal ions from aqueous solution by a novel cast PVA/TiO2 nanohybrid adsorbent functionalized with amine groups

Sorption of Cd(II), Ni(II) and U(VI) ions onto a novel cast PVA/TiO₂/APTES nanohybrid adsorbent with variations in adsorbent dose, pH, contact time, initial metal concentration and temperature has been investigated. The adsorbent were characterized by SEM and FTIR analysis. BET surface area, pore diameter and pore volume of adsorbent were 35.98 m² g⁻¹, 3.08 nm and 0.059 cm³ g⁻¹, respectively. The kinetic and equilibrium data were accurately described by the double-exponential and Freundlich models for all metals. The maximum sorption capacities were 49.0, 13.1 and 36.1 mg g⁻¹ for Cd(II), Ni(II) and U(VI) ions with pH of 5.5, 5 and 4.5, respectively. Thermodynamic studies showed that the sorption process was favored at higher temperature. The adsorbent can be easily regenerated after 5 cycles of sorption–desorption.     

Enhanced electrical properties in lead-free NBT–BT ceramics by series ST substitution

Comprehensive electrical properties of 0.94(Na_1/2Bi_1/2)TiO₃–0.06BaTiO₃ lead-free ceramics by doping series SrTiO₃ were investigated. High piezoelectric constant of 205 pC/N and electromechanical coupling factor of 0.34 were obtained due to the forming of the rhombohedral–tetragonal morphotropic phase boundary at x=0.02–0.06. Very large recoverable strain of 0.34% was obtained at x=0.10 due to the coexistence of ferroelectric and relaxor pseudocubic phases. A large electrocaloric effect (ΔT_max=1.71 K and ΔT/ΔE=0.34 K mm kV⁻¹ at 50 kV cm⁻¹) which determined by indirect measurements method was obtained at 120 °C at x=0.02, which is significantly higher than that of lead-free ferroelectric ceramics reported so far. Moreover, lower operating temperatures of 50 °C and 30 °C were proposed when x=0.10 and 0.20 with ΔT_max=0.79 K and 0.6 K, respectively. These properties added together indicate a promising material for applications in cooling systems and actuators.     

Flame atomic absorption spectrometric determination of Cd,Pb, and Cu in food samples after pre-concentration using 4-(2-thiazolylazo) resorcinol-modified activated carbon

This work aimed to develop a solid-phase extraction method using low-cost activated carbon produced from waste and modified with 4-(2-thiazolylazo) resorcinol for Cd(II), Pb(II), and Cu(II). The results showed that quantitative recovery of analytes was obtained at pH 6 with 3 M nitric acid as the eluent and a sample volume up to 1000 mL. The method was validated using certified reference material and addition-recovery tests. The limits of detection (LODs) for Pb(II), Cd(II), and Cu(II) were 2.03 μg L⁻¹, 0.15 μg L⁻¹, and 0.19 μg L⁻¹, respectively. The procedure was applied for determination of analytes in food samples.